EP0663459A1 - Appareil produisant de l'hydrogene et de l'oxygene - Google Patents

Appareil produisant de l'hydrogene et de l'oxygene Download PDF

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Publication number
EP0663459A1
EP0663459A1 EP93921076A EP93921076A EP0663459A1 EP 0663459 A1 EP0663459 A1 EP 0663459A1 EP 93921076 A EP93921076 A EP 93921076A EP 93921076 A EP93921076 A EP 93921076A EP 0663459 A1 EP0663459 A1 EP 0663459A1
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EP
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Prior art keywords
hydrogen
generating apparatus
oxygen generating
container
accordance
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EP93921076A
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German (de)
English (en)
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EP0663459A4 (fr
Inventor
Tadahiro Ohmi
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
    • H01M8/182—Regeneration by thermal means
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
    • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Definitions

  • the present invention relates to a hydrogen and oxygen generating apparatus, and, in greater detail, relates to a hydrogen and oxygen generating apparatus which consumes almost no fossil fuels, does not contaminate the global environment, and is capable of producing large amounts of highly pure hydrogen and oxygen at low costs.
  • Hydrogen energy is a clean form of energy which will be of increasing importance in the future; however, whether obtained as combustion energy, or as electrical energy in a fuel cell, greater energy can be obtained if oxygen is also present.
  • thermal cracking is caused at high temperatures in petrochemical complexes.
  • CnH 2n+2 ⁇ nCH2 + H2 This reaction also involves a number of side reactions, so that the purity of the hydrogen is low.
  • the production of oxygen is widely carried out by means of the fractional distillation of liquid air; however, separation of the oxygen from nitrogen, argon, and the like is difficult, and the costs involved are high.
  • Electrolysis is a commonly known method for the simultaneous production of hydrogen and oxygen; however, as the costs involved are dramatically higher than those of other methods, it can only be used for some uses requiring high purity (for example, semiconductor production). Development has proceeded in the use of natural sources of energy, such as solar energy and the like, in order to reduce the cost thereof; however,there have been problems in that it is difficult to obtain large amounts of power,and the initial costs thereof are high.
  • the present invention has an object thereof to provide a hydrogen and oxygen generating apparatus which uses almost no fossil fuels, does not contaminate the global environment, and is capable of producing highly pure hydrogen and oxygen in large amounts at low cost.
  • the hydrogen and oxygen generating apparatus in accordance with the present invention which solves the problems described above, is characterized in that: a solution prepared by adding, to a solvent which does not disassociate by itself, a substance which disassociates in this solvent, is contained in a container, the inner surface of which has corrosion resistance with respect to the solution; an anode having a small work function and a cathode having a large work function are immersed in the solution contained within the container so as to be mutually opposed; and a heat application mechanism for applying a predetermined amount of heat to the solution is provided.
  • the hydrogen and oxygen generating apparatus in accordance with the present invention is characterized in being provided with at least: a container, possessing an inner surface having corrosion resistance with respect to hydrogen fluoride containing water and, in some cases, having electrical insulation properties; a solution, which is stored within the container so as to be isolated from the atmosphere and which comprises a mixture of anhydrous hydrogen fluoride and water; an anode comprising a material having a small work function and possessing corrosion resistance with respect to hydrogen fluoride containing water, and a cathode comprising a material having a large work function and possessing corrosion resistance with respect to hydrogen fluoride containing water, which are immersed in the solution so as to be mutually opposed; a heat application mechanism for applying a predetermined amount of heat to the solution; and a mechanism for continuously suppling water to the solution.
  • FIG. 1 is a conceptual diagram which illustrates the principle of the present invention.
  • Figure 2 is a graph showing the relationship between the concentration of water in the hydrogen fluoride and the degree of dissociation.
  • Figure 3 is a conceptual diagram of a hydrogen and oxygen generating apparatus which depicts an example of the present invention.
  • Figure 4 is a graph showing the relationship between the conductivity of the hydrogen fluoride containing water and temperature.
  • Figure 5 is a conceptual diagram of a hydrogen and oxygen generating apparatus showing a modified example of the present invention.
  • Figure 6 is a conceptual diagram of a hydrogen and oxygen generating apparatus showing a modified example of the present invention.
  • Figure 7 is a conceptual diagram of a hydrogen and oxygen generating apparatus showing another modified example of the present invention.
  • Figure 8 is a conceptual diagram of a hydrogen and oxygen generating apparatus showing another example of the present invention.
  • liquid hydrogen fluoride is used as the solvent and water is used as the substance which is added thereto; however, the present invention is not limited thereto, and other substances to which the principle of the present invention discussed below can be applied are also included in the scope of the present invention.
  • an anode 11 comprising a material having a small work function and a cathode 12 comprising a material having a large work function are disposed in mutual opposition with a predetermined gap therebetween.
  • the anode 11 and the cathode 12 are connected via a load 10, and when the gap between the electrodes is filled with hydrogen fluoride containing water, electrons begin to flow via the load between electrodes from the anode having a small work function to the cathode having a large work function, so that a difference in potential is generated.
  • the load resistance is normally set to zero and the anode and cathode are directly connected by a wire.
  • the water dissolved in the hydrogen fluoride dissociates and forms H+ and OH ⁇ .
  • the H+ ions and OH ⁇ ions move to the cathode and anode sides, respectively, and based on the following reactions: 4H+ + 4e ⁇ ⁇ 2H2 (1) 4OH ⁇ ⁇ O2 + 2H2O + 4e ⁇ (2) hydrogen gas and oxygen gas are generated and a current flows externally. That is to say, at the cathode, electrons are donated to the H+ ions and H2 is generated, while at the anode, electrons are accepted from the OH ⁇ ions, and O2 is generated.
  • the H2O which is generated at the anode again receives thermal energy in the hydrogen fluoride solution, and dissociates into H+ and OH ⁇ ions.
  • the present inventors have studied the relationship between the degree of ion dissociation of water and the concentration of the water in liquid hydrogen fluoride, which remains in a liquid state within a temperature range of from -83.5°C to +19.5°C at atmospheric pressure, and have discovered that in contrast to cases in which water is present in other solutions, when water is present in hydrogen fluoride, the degree of dissociation thereof is extremely high. This relationship is shown in Figure 2 with respect to the case in which the hydrogen fluoride solution was maintained at a temperature of 0°C.
  • the electrical conductivity of the liquid hydrogen fluoride was 5 ⁇ 10 ⁇ 3 s ⁇ cm ⁇ 1, 3 ⁇ 10 ⁇ 2 s ⁇ cm ⁇ 1, and 1 ⁇ 10 ⁇ 1 s ⁇ cm ⁇ 1, respectively, at H2O concentrations of 180 ppm, 1,800 ppm, and 18,000 ppm (1.8%).
  • H2O concentration 180 ppm, 1,800 ppm, and 18,000 ppm (1.8%).
  • reference 1 indicates a hydrogen and oxygen generator; anode 11 and cathode 12 are attached to a container 13, the inner surface of which has been subjected to insulation processing, and the oxygen and hydrogen generated at each electrode are divided by partition 14 so that they do not mix, are sent out from respective exits as mixed liquids with anhydrous hydrogen fluoride, are separated into gases and liquids in in gas/liquid separation tanks 15 and 15' along separate lines, and the anhydrous hydrogen fluoride is separated by condensation in coolers 16 and 16'. Furthermore, where necessary, deoxidation processing 17 and 17' and dehydration processing 18 and 18' are conducted. Extension wires 19 and 20 are attached to each electrode, and the current generated is supplied to the exterior.
  • Reference 2 indicates a water mixing chamber for replenishing the water in the hydrogen fluoride which was depleted by being converted into hydrogen and oxygen.
  • the addition of water may be accomplished by means of methods such as a liquid pump, water vapor injection, membrane permeation, or the like.
  • Conductometers 21 are provided before and after the water mixing chamber, and by means of measuring the water concentration in the hydrogen fluoride within the system, the amount of water supplied can be controlled.
  • Reference 3 indicates a heat exchanger (providing a heating/cooling function)
  • references 4 and 4' indicate circulation pumps (force feeding mechanisms) for circulating the solution of hydrogen fluoride containing water
  • reference 5 indicates piping, the inner surface of which has been subjected to insulation processing.
  • a solution of hydrogen fluoride containing water at a predetermined concentration is placed in the system shown in Figure 3.
  • the apparatus as a whole be constructed so as to be resistant to pressures on a level of 70kg/cm2.
  • the reason for this is that the critical temperature of the hydrogen fluoride solution is 188°C, and the critical pressure thereof is 66.16 kg/cm2.
  • the hydrogen fluoride is cooled in the heating and cooling apparatus 3 and the temperature is maintained at a predetermined temperature within a range of approximately 20°C - ⁇ 30°C.
  • the changes in conductivity of the hydrogen fluoride with respect to temperature are shown in Figure 4.
  • Lines A, B, and C show the changes in temperature in the cases in which the amount of water is, respectively, 10 ppm, 35 ppm, and 135 ppm.
  • the lower limit of the operating temperatures be set at approximately -30°C.
  • the H20 added to the anhydrous hydrofluoric acid in water mixing chamber 2 immediately dissociates into ions.
  • H2O ⁇ H+ + OH ⁇ + Q Q is the heat of reaction
  • the dissociation of the water is an endothermic reaction, so that heat is taken from the hydrogen fluoride liquid, and as circulation is repeated, the temperature of the liquid decreases.
  • the electric conductivity of the hydrogen fluoride declines, and the amount of hydrogen and oxygen which can be obtained at gas generator 1 decreases.
  • heat exchanger 3 a heat application mechanism for applying heat to the hydrogen fluoride liquid
  • the vapor pressure of the hydrogen fluoride liquid at various temperatures is shown in Table 1. If pressures of 2.8 kg/cm2 and 10.8 kg/cm2 or more, respectively, are applied, then the hydrogen fluoride will remain in a liquid state even if temperatures of, respectively, 50°C and 100°C are attained.
  • the cooler is only required in the initial period of operation of the system, so that it is not particularly necessary to install a dedicated unit. Furthermore, with respect to the source of the thermal energy applied by the heat application means, in addition to solar energy, geothermal energy, and the waste thermal energy of incinerators, it is also possible to employ the thermal energy of sea or river water or the like, as the operational temperatures are low.
  • the work functions of Pt and LaB6 are 5.64 - 5.93 eV and 2.66 - 2.76 eV, respectively, so that the difference in the work functions is on the level of 2.88 - 3.27 eV, and current flows efficiently to the exterior and oxygen and hydrogen are also efficiently generated.
  • the electrical resistivity ⁇ 1 of hydrogen fluoride solutions containing 300 ppm and 1.8% of water at a temperature of 0°C are approximately 125 ⁇ cm, and 10 ⁇ cm, respectively.
  • the electrical resistivity ⁇ 0 of a hydrogen fluoride solution containing almost no water has not yet been determined; however, it can be assumed from Figure 2 that this value would be approximately 107 ⁇ cm or more. If the ion reaction at the anode and cathode is to be carried out efficiently to approximately 100%, then it is desirable that the current density J (A/cm2) be set to within a range of 10 mA/cm2 to 100 mA/cm2.
  • the amount of hydrogen and oxygen generated is determined by the amount of current flowing between the electrodes. According, in order to obtain large amounts of hydrogen and oxygen, it is necessary to directly connect the anode and cathode, to reduce the distance between electrodes as much as possible, and to conduct operations using as large an amount of water in the hydrogen fluoride as possible.
  • the interior of the container is partitioned by insulating dividing plates (for example, fluorine resins such as PTFE, PFA, and the like) 51, 51', 51'', ... , 52, 52', 52'',..., 53, and 54, and by electrodes, so that one chamber comprises a unit cell containing partitions.
  • insulating dividing plates for example, fluorine resins such as PTFE, PFA, and the like
  • the electrode 11 on the left-hand side of the Figure is an electrode having a small work function (for example, LaB6, TiN, or the like), and the electrode 12 on the right-hand side is an electrode having a large work function (for example, Pt, Pd, Au, Ni, or the like), and the electrodes provided therebetween are electrodes in which, for example, LaB6 (11, 11',11'' ...) and Pt (12, 12', 12'' ...) are affixed to one another. Furthermore, it is of course the case that electrodes in which Pt and LaB6 are coated on or affixed to the front and rear of a metal such as stainless steel or the like may also be employed. If each cell has the same structure, and the same amount of hydrogen fluoride solution is caused to flow, then the amount of hydrogen and oxygen generated will be that generated in the case of one cell multiplied by the number of stages.
  • a small work function for example, LaB6, TiN, or the like
  • the electrode 12 on the right-hand side is an
  • dividing plates 52, 52',... which are constructed using a fluorine resin or the like, are provided; however, if the voltage drop in the hydrogen fluoride solution between electrodes can be sufficiently disregarded, then these dividing plates are not necessary. Furthermore, since the H+ and OH ⁇ formed by means of the electrode reaction in the hydrogen fluoride are converted into H2 and O2, the dividing plates 51, 51',... are necessary for the separation thereof.
  • another method for providing multiple stages is that in which a plurality of unit cells are connected in a manner identical to that shown in Figure 5 to form a unit 61, and as shown in Figure 7, the entrances 60 of units 61, with the main input pipe 63 and the main output pipe 64, are formed into a circulating system via a water mixing chamber (not depicted in the Figure) and a force feeding mechanism (not depicted in the Figure).
  • a water mixing chamber not depicted in the Figure
  • a force feeding mechanism not depicted in the Figure
  • the introduction port 68 into the main input pipe 63 is provided at the left-hand side as shown in Figure 7, it is desirable that the exhaust port 69 of the main output pipe 64 be provided at the right-hand side, as shown in Figure 7, from the point of view of uniform supply of solution to each unit 61.
  • each unit 61 is made freely attachable to and detachable from the main input pipe 63 and the main output pipe 64, then in the case in which any of the units is damaged, only that unit which is damaged can be removed and repaired without a stoppage in the operation of the system as a whole.
  • a circuit (not depicted in the Figure) which automatically connects the electrodes of both units adjacent to the unit which is being repaired at this time may be provided. If branch valves (three way valves) are provided at the entrance 60 and the exit 65 of each unit 61, then it is possible to facilitate the removal and exchange of the solution in each unit 61. Furthermore, flow meters or the like may be provided at entrances 60 and exits 65.
  • the solvent in the present invention is a solvent which does not dissociate by itself, and the substance which is added to this solvent is a substance which dissociates in the solvent.
  • Examples of such a combination include, for example, a combination of hydrogen fluoride as the solvent, and water as the added substance.
  • the concentration of the added substance varies depending on the concrete combination of the solvent and added substance; however, in the case, for example, of the combination of hydrogen fluoride and water, the amount of water added is preferably 2% or less. If the amount is greater than this, the liquid would not be one in which water was added to anhydrous hydrogen fluoride. However, 10 ppm or more is necessary so that the resistivity does not become too large, as seen in Figure 2.
  • anhydrous hydrogen fluoride itself does not have strong corrosivity; however, when water is added thereto, the corrosivity increases, and when the amount of water added exceeds approximately 2%, the anode and cathode described hereinbelow become corroded. Accordingly, it is preferable that the amount of water be 2% or less from the point of view of preventing this corrosion. However, when the amount of water is 10 ppm or less, 100% of the water dissociates, but the ion concentration is low, so that the electrical resistivity of the hydrogen fluoride solution becomes excessively large, having a value of a few k ⁇ cm or more, and an efficient hydrogen and oxygen generating system cannot be constructed.
  • the reason for the use of a solvent which itself does not dissociate is as follows. It is preferable that electrodes be disposed in multiple stages in the hydrogen and oxygen generating apparatus, as shown in Figure 5, in order to obtain large amounts of gas. Moreover, if the solvent were to dissociate, the ions produced as a result of this dissociation would themselves carry the load, so that a current would flow in the interval with the other electrode. This would result in a loss of power. Furthermore, when the solvent itself ionizes and turns to gas as a result of the ion reaction at the electrodes, stable power generation cannot be maintained.
  • resistivity M ⁇ cm 25°C
  • pcs/cc 18 particles
  • TOC ⁇ gC/l
  • dissolved oxygen ⁇ gO/l
  • the difference in work function between the anode and cathode which are used in the present invention be as great as possible. This is so that a current can be efficiently caused to flow to the exterior and so that hydrogen and oxygen can be efficiently generated.
  • hydrogen fluoride which contains water has high corrosivity, as described above, it is necessary that the materials used possess corrosion resistance. Examples of such materials include, for example, with respect to the anode, Pt, Au, Ni, Pd, and the like.
  • examples of materials used for the cathode include, for example, LaB6, TiN, NbC, W2C, ZrN, ZrC, Cs, or the like. It is of course sufficient if only that portion of the electrode which is in contact with the hydrogen fluoride solution containing water comprises such materials; accordingly, electrodes in which an appropriate material is used as a base material, and the surfaces thereof are clad in such corrosion resistant materials, may be employed.
  • oxide films and the like although extremely thin, commonly form on the surfaces of such materials, and impurities are deposited thereon.
  • the presence of such oxide films or impurities interferes with the reaction at the electrode surface.
  • hydrogen fluoride containing water is used as the solution, so that simply by immersing the electrodes in this solution, it is possible to remove such oxide films or impurities, and furthermore, it is possible to expose the active surfaces of the electrodes, and this constitutes an important advantage. This is one reason why it is preferable to employ a hydrogen fluoride solution containing water in the present invention.
  • the distance between the opposing electrodes be as small as possible. If the distance is large, the current value will decrease as a result of the electrical resistance possessed by the hydrogen fluoride solution containing water between the electrodes, and it becomes impossible to generate large amounts of current. Concretely, a distance of 1 cm or less is preferable, and a distance of 1 mm or less further preferable.
  • the lower limit may be appropriately determined in consideration of the pressure loss when the solution is circulated or the difficulty of construction; however, a value within a range of 0.1 mm - 0.3 mm is preferable.
  • the container which is employed to hold the hydrogen fluoride solution containing water has an interior (that is to say, the portion in which the hydrogen fluoride solution is contained) which is isolated from the atmosphere. If the hydrogen fluoride liquid comes into contact with the atmosphere, it will absorb moisture from the atmosphere. Accordingly, it is isolated from the atmosphere in order to prevent this.
  • any material may be used for this container, insofar as the material possesses corrosion resistance with respect to hydrogen fluoride containing water.
  • a fluorine resin (more concrete examples thereof being PTFE, PFA, or the like) may be employed. It is of course the case that only those portions which are in contact with the hydrogen fluoride solution containing water need comprise, for example, PTFE; accordingly, an inner surface comprising, for example, stainless steel may be lined with PTFE or PFA.
  • the container may comprise a metal material, on the surface of which is formed a fluoride passivated film approximately satisfying a stoichiometric ratio.
  • a container in which a metal surface, having formed thereon a fluoride passivated film which approximately satisfies a stoichiometric ratio, is lined with a fluorine resin is most preferable.
  • the use of iron, stainless steel (in particular SUS 316L), aluminum alloy, or magnesium alloy is preferable as the metallic material forming the base material on which a fluoride passivated film is formed.
  • the fluoride passivated films (FeF2, AlF3, MgF2) which are formed on the metallic materials are extremely fine, exhibit extremely high corrosion resistance with respect to hydrogen fluoride containing water, and possess superior electric insulation properties.
  • Such fluoride passivated films may employ the formation technology disclosed in, for example, Japanese Patent Application, First Publication, No. Hei 2-270964.
  • the boiling point of hydrogen fluoride is 19.6°C, so that at normal temperatures, there is a possibility that it will change to a gaseous state.
  • Pressure may be applied in order to prevent gasification. For example, if a pressure of approximately 11 kg/cm2 is applied, gasification can be prevented even at a temperature of 100°C. This is as previously described in the "Function" section.
  • reference 1 indicates a hydrogen and oxygen generator; an anode 11 comprising LaB6 and a cathode 12 comprising Pt are attached to a stainless steel container, the surface of which is lined with PFA.
  • the electrodes have a length of 15 cm and a width of 10 cm, and the gap between electrodes was set to 100 ⁇ m.
  • References 19 and 20 indicate extension wires for extracting current.
  • Reference 2 indicates a water mixing chamber; an amount of water identical to that which was converted into hydrogen and oxygen and thus consumed is introduced via a volumetric pump, and this is completely mixed.
  • Reference 3 indicates a heating and cooling apparatus.
  • Reference 4 indicates a pump for circulating hydrogen fluoride solution to water mixing chamber 2, heating and cooling mechanism 3, and in the piping.
  • Reference 6 indicates a thermometer.
  • thermometer 6 was fed back to the heating and cooling mechanism and the temperature of the hydrogen fluoride solution was maintained at 0°C.
  • the amount of water contained in the hydrogen fluoride was verified by means of the conductivity at water mixing chamber 2 and the conductometers before and after this chamber.
  • Figure 8 shows a second embodiment of the present invention.
  • reference 11 is an electrode comprising LaB6, and in the central electrode, the left-hand side 11' comprises Pt, while the right-hand side 12' comprises LaB6.
  • References 71 and 72 indicate insulating dividing plates which separate the cells; in the present embodiment, PTFE was used therefor. All other references are identical to those in Figure 3.
  • the size of the electrodes was set to 15 ⁇ 10 cm, the distance between electrodes was set to 100 ⁇ m, and the length of dividing plates 71 and 72 was set to 5 cm and 15 cm, respectively.
  • the hydrogen and oxygen generating apparatus in accordance with the present invention may be reduced or increased in size based on the number of electrodes. Because a high temperature heat source is not required, the effective use of energy which cannot presently be effectively used as an energy source, such as solar energy, waste heat energy, sea water, river water, and various kinds of waste water having somewhat high temperatures, becomes possible.
EP93921076A 1992-09-28 1993-09-28 Appareil produisant de l'hydrogene et de l'oxygene. Withdrawn EP0663459A4 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP4258682A JPH06108279A (ja) 1992-09-28 1992-09-28 水素酸素発生装置
JP258682/92 1992-09-28
PCT/JP1993/001379 WO1994008070A1 (fr) 1992-09-28 1993-09-28 Appareil produisant de l'hydrogene et de l'oxygene

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Publication Number Publication Date
EP0663459A1 true EP0663459A1 (fr) 1995-07-19
EP0663459A4 EP0663459A4 (fr) 1995-11-29

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EP93921076A Withdrawn EP0663459A4 (fr) 1992-09-28 1993-09-28 Appareil produisant de l'hydrogene et de l'oxygene.

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JP (1) JPH06108279A (fr)
WO (1) WO1994008070A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0810682A3 (fr) * 1996-05-30 2004-08-18 Toyota Jidosha Kabushiki Kaisha Dispositif et procédé de générateur à piles à combustible
US20110006544A1 (en) * 2007-12-10 2011-01-13 David Geurts Hydrogen Generator

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008001932A (ja) * 2006-06-21 2008-01-10 Sumitomo Electric Ind Ltd 電解用電極
JP5429789B2 (ja) * 2009-04-21 2014-02-26 国立大学法人東北大学 電気透析装置

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DE2045350A1 (de) * 1970-09-14 1972-03-16 Saline Power Systems Inc Primärelement mifAnode aus einer Magnesium-Lithium-Legierung
EP0057669A2 (fr) * 1981-02-02 1982-08-11 Michael Graetzel Produit destiné à être utilisé comme photocatalyseur et utilisation de ce produit

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JPS5469574A (en) * 1977-11-14 1979-06-04 Agency Of Ind Science & Technol High-temperature electrolyzing method for water and apparatus thereof
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JPS6142908Y2 (fr) * 1980-03-11 1986-12-05
JPS6022070B2 (ja) * 1981-09-22 1985-05-30 ペルメレツク電極株式会社 酸性溶液電解用陰極及びその製造方法
JP2631571B2 (ja) * 1990-04-26 1997-07-16 義郎 中松 高能率電解エネルギ装置

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DE2045350A1 (de) * 1970-09-14 1972-03-16 Saline Power Systems Inc Primärelement mifAnode aus einer Magnesium-Lithium-Legierung
EP0057669A2 (fr) * 1981-02-02 1982-08-11 Michael Graetzel Produit destiné à être utilisé comme photocatalyseur et utilisation de ce produit

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Title
HEISE G. W. 'The Primary Battery, Vol. 1, The Electrochemical Series, Chapter 1, The Simple Volta Battery, pages 3-13' 1971 , WILEY , NY * page 4; figure 1.2 * * page 4, paragraph 1 - page 5, paragraph 1 * *
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, vol.137, no.3, March 1990, MANCHESTER, NEW HAMPSHIRE US pages 790 - 794 OHMI T. 'Conductivity and Dissociation Equilibrium of Extremely Anhydrous Hydrogen Fluoride' *
See also references of WO9408070A1 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0810682A3 (fr) * 1996-05-30 2004-08-18 Toyota Jidosha Kabushiki Kaisha Dispositif et procédé de générateur à piles à combustible
US20110006544A1 (en) * 2007-12-10 2011-01-13 David Geurts Hydrogen Generator
US8864974B2 (en) * 2007-12-10 2014-10-21 Printer Ribbon Inkers P.R.I. Limited Hydrogen generator

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EP0663459A4 (fr) 1995-11-29
WO1994008070A1 (fr) 1994-04-14
JPH06108279A (ja) 1994-04-19

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